Dual-Functional Tamm-Dancoff Approximation: A Convenient Density Functional Method that Correctly Describes S1/S0 Conical Intersections

Yinan Shu, Kelsey A. Parker, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

Time-dependent Kohn-Sham density functional theory has been used successfully to compute vertical excitation energies, especially for large molecular systems. However, the lack of double excitation character in the excited amplitudes produced by linear response in the adiabatic approximation holds it back from broader applications in photochemistry; for example, it shows (3N - 7)-dimensional conical intersection seams (where N is the number of atoms) between ground and excited states, although the correct dimensionality is 3N - 8. In this letter, we present a new, conceptually simple, easy-to-implement, and easy-to-use way to employ time-dependent Kohn-Sham density functional theory that has global accuracy comparable with the conventional single-functional version and that recovers the double cone topology of the potential energy surfaces at S1/S0 conical intersection seams. The new method is called the dual-functional Tamm-Dancoff approximation (DF-TDA).

Original languageEnglish (US)
Pages (from-to)2107-2112
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume8
Issue number10
DOIs
StatePublished - May 18 2017

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0015997.

Publisher Copyright:
© 2017 American Chemical Society.

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